Bravais lattice

The Bravais lattice is the basic building block from which all crystals can be constructed. The concept originated as a topological problem of finding the number of different ways to arrange points in space where each point would have an identical “atmosphere”. That is each point would be surrounded by an identical set of points as any other point, so that all points would be indistinguishable from each other. Mathematician Auguste Bravais discovered that there were 14 different collections of the groups of points, which are known as Bravais lattices. These lattices fall into seven different "crystal systems”, as differentiated by the relationship between the angles between sides of the “unit cell” and the distance between points in the unit cell. The unit cell is the smallest group of atoms, ions or molecules that, when repeated at regular intervals in three dimensions, will produce the lattice of a crystal system. The “lattice parameter” is the length between two points on the corners of a unit cell. Each of the various lattice parameters are designated by the letters a, b, and c. If two sides are equal, such as in a tetragonal lattice, then the lengths of the two lattice parameters are designated a and c, with b omitted. The angles are designated by the Greek letters α, β, and γ, such that an angle with a specific Greek letter is not subtended by the axis with its Roman equivalent. For example, α is the included angle between the b and c axis.

Table 1 shows the various crystal systems, while Figure 1 shows the 14 Bravais lattices. It is important to distinguish the characteristics of each of the individual systems. An example of a material that takes on each of the Bravais lattices is shown in Table 2.

The cubic lattice is the most symmetrical of the systems. All the angles are equal to 90°, and all the sides are of the same length (a = b = c). Only the length of one of the sides (a) is required to describe this system completely. In addition to simple cubic, the cubic lattice also includes body-centered cubic and face-centered cubic (Figure 1). Body-centered cubic results from the presence of an atom (or ion) in the center of a cube, in addition to the atoms (ions) positioned at the vertices of the cube. In a similar manner, a face-centered cubic requires, in addition to the atoms (ions) positioned at the vertices of the cube, the presence of atoms (ions) in the center of each of the cubes face.

The tetragonal lattice has all of its angles equal to 90°, and has two out of the three sides of equal length (a = b). The system also includes body-centered tetragonal (Figure 1).

In an orthorhombic lattice all of the angles are equal to 90°, while all of its sides are of unequal length. The system needs only to be described by three lattice parameters. This system also includes body-centered orthorhombic, base-centered orthorhombic, and face-centered orthorhombic (Figure 1). A base-centered lattice has, in addition to the atoms (ions) positioned at the vertices of the orthorhombic lattice, atoms (ions) positioned on just two opposing faces.

The rhombohedral lattice is also known as trigonal, and has no angles equal to 90°, but all sides are of equal length (a = b = c), thus requiring only by one lattice parameter, and all three angles are equal (α = β = γ).

A hexagonal crystal structure has two angles equal to 90°, with the other angle ( γ) equal to 120°. For this to happen, the two sides surrounding the 120° angle must be equal (a = b), while the third side (c) is at 90° to the other sides and can be of any length.

The monoclinic lattice has no sides of equal length, but two of the angles are equal to 90°, with the other angle (usually defined as β) being something other than 90°. It is a tilted parallelogram prism with rectangular bases. This system also includes base-centered monoclinic (Figure 1).

In the triclinic lattice none of the sides of the unit cell are equal, and none of the angles within the unit cell are equal to 90°. The triclinic lattice is chosen such that all the internal angles are either acute or obtuse. This crystal system has the lowest symmetry and must be described by 3 lattice parameters (a, b, and c) and the 3 angles (α, β, and γ).

Atom positions, crystal directions and Miller indices

The structure of a crystal is defined with respect to a unit cell. As the entire crystal consists of repeating unit cells, this definition is sufficient to represent the entire crystal. Within the unit cell, the atomic arrangement is expressed using coordinates. There are two systems of coordinates commonly in use, which can cause some confusion. Both use a corner of the unit cell as their origin. The first, less-commonly seen system is that of Cartesian or orthogonal coordinates (X, Y, Z). These usually have the units of Angstroms and relate to the distance in each direction between the origin of the cell and the atom.

Crystal directions

The designation of the individual vectors within any given crystal lattice is accomplished by the use of whole number multipliers of the lattice parameter of the point at which the vector exits the unit cell. The vector is indicated by the notation [hkl], where h, k, and l are reciprocals of the point at which the vector exits the unit cell. The origination of all vectors is assumed defined as [000]. For example, the direction along the a-axis according to this scheme would be [100] because this has a component only in the a-direction and no component along either the b or c axial direction. A vector diagonally along the face defined by the a and b axis would be [110], while going from one corner of the unit cell to the opposite corner would be in the [111] direction. Figure 2 shows some examples of the various directions in the unit cell. The crystal direction notation is made up of the lowest combination of integers and represents unit distances rather than actual distances. A [222] direction is identical to a [111], so [111] is used. Fractions are not used. For example, a vector that intercepts the center of the top face of the unit cell has the coordinates x = 1/2, y = 1/2, z = 1. All have to be inversed to convert to the lowest combination of integers (whole numbers); i.e., [221] in Figure 2. Finally, all parallel vectors have the same crystal direction, e.g., the four vertical edges of the cell shown in Figure 2 all have the crystal direction [hkl] = [001].

Crystal directions may be grouped in families. To avoid confusion there exists a convention in the choice of brackets surrounding the three numbers to differentiate a crystal direction from a family of direction. For a direction, square brackets [hkl] are used to indicate an individual direction. Angle brackets <hkl> indicate a family of directions. A family of directions includes any directions that are equivalent in length and types of atoms encountered. For example, in a cubic lattice, the [100], [010], and [001] directions all belong to the <100> family of planes because they are equivalent. If the cubic lattice were rotated 90°, the a, b, and c directions would remain indistinguishable, and there would be no way of telling on which crystallographic positions the atoms are situated, so the family of directions is the same. In a hexagonal crystal, however, this is not the case, so the [100] and [010] would both be <100> directions, but the [001] direction would be distinct. Finally, negative directions are identified with a bar over the negative number instead of a minus sign.

Crystal planes

Planes in a crystal can be specified using a notation called Miller indices. The Miller index is indicated by the notation [hkl] where h, k, and l are reciprocals of the plane with the x, y, and z axes. To obtain the Miller indices of a given plane requires the following steps:

Step 1. The plane in question is placed on a unit cell.

Step 2. Its intercepts with each of the crystal axes are then found.

Step 3. The reciprocal of the intercepts are taken.

Step 4. These are multiplied by a scalar to insure that is in the simple ratio of whole numbers.

For example, the face of a lattice that does not intersect the y or z axis would be (100), while a plane along the body diagonal would be the (111) plane. An illustration of this along with the (111) and (110) planes is given in Figure 3.

As with crystal directions, Miller indices directions may be grouped in families. Individual Miller indices are given in parentheses (hkl), while braces {hkl} are placed around the indices of a family of planes. For example, (001), (100), and (010) are all in the {100} family of planes, for a cubic lattice.

Description of crystal structures

Crystal structures may be described in a number of ways. The most common manner is to refer to the size and shape of the unit cell and the positions of the atoms (or ions) within the cell. However, this information is sometimes insufficient to allow for an understanding of the true structure in three dimensions. Consideration of several unit cells, the arrangement of the atoms with respect to each other, the number of other atoms they in contact with, and the distances to neighboring atoms, often will provide a better understanding. A number of methods are available to describe extended solid-state structures. The most applicable with regard to elemental and compound semiconductor, metals and the majority of insulators is the close packing approach.

Close packed structures: hexagonal close packing and cubic close packing

Many crystal structures can be described using the concept of close packing. This concept requires that the atoms (ions) are arranged so as to have the maximum density. In order to understand close packing in three dimensions, the most efficient way for equal sized spheres to be packed in two dimensions must be considered.

The most efficient way for equal sized spheres to be packed in two dimensions is shown in Figure 4, in which it can be seen that each sphere (the dark gray shaded sphere) is surrounded by, and is in contact with, six other spheres (the light gray spheres in Figure 4). It should be noted that contact with six other spheres the maximum possible is the spheres are the same size, although lower density packing is possible. Close packed layers are formed by repetition to an infinite sheet. Within these close packed layers, three close packed rows are present, shown by the dashed lines in Figure 4.

The most efficient way for equal sized spheres to be packed in three dimensions is to stack close packed layers on top of each other to give a close packed structure. There are two simple ways in which this can be done, resulting in either a hexagonal or cubic close packed structures.

Hexagonal close packed

If two close packed layers A and B are placed in contact with each other so as to maximize the density, then the spheres of layer B will rest in the hollow (vacancy) between three of the spheres in layer A. This is demonstrated in Figure 5. Atoms in the second layer, B (shaded light gray), may occupy one of two possible positions (Figure 5a or b) but not both together or a mixture of each. If a third layer is placed on top of layer B such that it exactly covers layer A, subsequent placement of layers will result in the following sequence ...ABABAB.... This is known as hexagonal close packing or hcp.

The hexagonal close packed cell is a derivative of the hexagonal Bravais lattice system (Figure 1) with the addition of an atom inside the unit cell at the coordinates (1/3,2/3,1/2). The basal plane of the unit cell coincides with the close packed layers (Figure 6). In other words the close packed layer makes-up the {001} family of crystal planes.

The “packing fraction” in a hexagonal close packed cell is 74.05%; that is 74.05% of the total volume is occupied. The packing fraction or density is derived by assuming that each atom is a hard sphere in contact with its nearest neighbors. Determination of the packing fraction is accomplished by calculating the number of whole spheres per unit cell (2 in hcp), the volume occupied by these spheres, and a comparison with the total volume of a unit cell. The number gives an idea of how “open” or filled a structure is. By comparison, the packing fraction for body-

centered cubic (Figure 1) is 68% and for diamond cubic (an important semiconductor structure to be described later) is it 34%.

Cubic close packed: face-centered cubic

In a similar manner to the generation of the hexagonal close packed structure, two close packed layers are stacked (Figure 4) however, the third layer (C) is placed such that it does not exactly cover layer A, while sitting in a set of troughs in layer B (Figure 7), then upon repetition the packing sequence will be ...ABCABCABC.... This is known as cubic close packing or ccp.

The unit cell of cubic close packed structure is actually that of a face-centered cubic (fcc) Bravais lattice. In the fcc lattice the close packed layers constitute the {111} planes. As with the hcp lattice packing fraction in a cubic close packed (fcc) cell is 74.05%. Since face centered cubic or fcc is more commonly used in preference to cubic close packed (ccp) in describing the structures, the former will be used throughout this text.

Coordination number

The coordination number of an atom or ion within an extended structure is defined as the number of nearest neighbor atoms (ions of opposite charge) that are in contact with it. A slightly different definition is often used for atoms within individual molecules: the number of donor atoms associated with the central atom or ion. However, this distinction is rather artificial, and both can be employed.

The coordination numbers for metal atoms in a molecule or complex are commonly 4, 5, and 6, but all values from 2 to 9 are known and a few examples of higher coordination numbers have been reported. In contrast, common coordination numbers in the solid state are 3, 4, 6, 8, and 12. For example, the atom in the center of body-centered cubic lattice has a coordination number of 8, because it touches the eight atoms at the corners of the unit cell, while an atom in a simple cubic structure would have a coordination number of 6. In both fcc and hcp lattices each of the atoms have a coordination number of 12.